US8883258B2 - Protective coating of silver - Google Patents

Protective coating of silver Download PDF

Info

Publication number
US8883258B2
US8883258B2 US12/162,051 US16205107A US8883258B2 US 8883258 B2 US8883258 B2 US 8883258B2 US 16205107 A US16205107 A US 16205107A US 8883258 B2 US8883258 B2 US 8883258B2
Authority
US
United States
Prior art keywords
silver
coating
thin coating
product
article
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US12/162,051
Other languages
English (en)
Other versions
US20090004386A1 (en
Inventor
Milja Makela
Pekka Soininen
Sami Sneck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beneq Oy
Original Assignee
Beneq Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=35953681&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US8883258(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Beneq Oy filed Critical Beneq Oy
Assigned to BENEQ OY reassignment BENEQ OY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MAKELA, MILJA, SNECK, SAMI, SOININEN, PEKKA
Publication of US20090004386A1 publication Critical patent/US20090004386A1/en
Application granted granted Critical
Publication of US8883258B2 publication Critical patent/US8883258B2/en
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/005—Coating layers for jewellery
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45555—Atomic layer deposition [ALD] applied in non-semiconductor technology

Definitions

  • the present invention relates to a method for coating silver products, and more particularly to a method according to the preamble of claim 1 coating silver.
  • Industrial atmospheres and natural digestive processes are important sources for the tarnishing of silver.
  • sulphides, oxides or carbonates are formed on the surface of silver.
  • the tarnishing of silver and silverware is a problem for example for the utility article, jewelry and giftware industries as well as to the end users of the silver products. Tarnishing degrades the appearance of the product as a layer or spots of black or dark grey colour are formed. It can be removed but this is usually a laborious process, and the process may affect the appearance of the product negatively.
  • the tarnishing of the silver reduces the optical properties, such as reflectivity, of silver and silver products and parts.
  • One existing method for preventing tarnishing comprises using silver alloys that are designed with resistance to oxidation and involve the mixing of special additives, such as silicon or germanium, with silver.
  • Another existing method for preventing tarnishing comprises coating pure silver using rhodium.
  • One of the problems associated with the above arrangement using silver alloys is that the method requires all factors to be carefully controlled during manufacture, like using extremely pure new metal and accurate temperature control in melting and annealing. As a result, the manufacturing process and the equipment to carry out the process are very expensive to set up. The cost is also prohibitive in the method for coating silver with rhodium. Further, the rhodium coating has a blue-white shade, and thus a silver product coated with rhodium may become visually different from pure silver.
  • An object of the present application is to provide a method so as to alleviate the above disadvantages.
  • the objects of the application are achieved by a method according to the characterizing portion of claim 1 . Therefore the present invention is characterized by applying a thin coating of protective material on at least a part of the surface of a silver product, article or part using an ALD (Atomic Layer Deposition) method.
  • ALD Atomic Layer Deposition
  • thin layer means in this context a layer having thickness between 1 nm and 1 ⁇ m, preferably between 1 and 100 nm, and most preferably approximately 2-20 nm.
  • a thin film coating is deposited on the surface of a silver object.
  • silver is coated with one or more molecule layers of aluminium oxide Al 2 O 3 .
  • Trimethyl aluminium (CH 3 ) 3 Al may be used as a precursor and water H 2 O as an oxygen source.
  • the thickness of the generated thin film per one ALD cycle is about 0.1 nm and the coating is carried out in a temperature of about 200° C.
  • the coating generated by the method is thin, dense, smooth and substantially colourless, and it precisely follows conformally the shapes, also three dimensional shapes, of the silver object without thickness variations in the coating.
  • the generated coating is compatible with foodstuffs.
  • the consumption of the coating material is low, and thus coating costs may be reduced.
  • the thickness of the coating layer may be controlled by varying the number of molecule layers in the coating.
  • the coating process is not sensitive to minor changes in the process parameters, and thus the repeatability of the method is good. This thin layer is sufficient for preventing the tarnishing of the silver, but does not affect the appearance of the silver product, as the conventional coating methods.
  • the coating may be so thin that human eye cannot see it.
  • Such a uniform layer is not possible to be provided on a three dimensional object for example with CVD method (Chemical Vapour Deposition) or PVD (Physical Vapour Deposition) method, since the coating process may not be controlled in such a detail as with ALD method.
  • CVD and other similar methods also require that the coated object have to be rotated for providing coating material over the whole surface of the three dimensional object.
  • FIG. 1 is a schematic representation of the coating process of silver with aluminium oxide according to the solution of the present application
  • FIG. 2 is a schematic representation of the structure of the coating according to the solution of the present application.
  • Industrial atmospheres and natural digestive processes are important sources for the tarnishing of silver.
  • sulphides, oxides or carbonates are formed on the surface of silver.
  • Tarnishing degrades the appearance of the product as a layer or spots of black or dark grey colour are formed.
  • the tarnishing of the silver reduces the optical properties, such as reflectivity, of silver and silver products and parts.
  • a thin coating may be provided on the surfaces of the silver product.
  • the coating should be sufficiently thin for preventing the change of the appearance of the silver product, but sufficiently thick to provide good passivation and/or protection against tarnishing.
  • This kind of thin coating may be applied on the surfaces of a silver product preferably by using Atomic Layer Deposition (ALD).
  • ALD Atomic Layer Deposition
  • Atomic Layer Deposition is a thin film technique that allows thin film coatings that have a nanoscale thickness to be manufactured.
  • ALD technique may also be called ALC (Atomic Layer Coating) technique or ALE (Atomic Layer Epitaxy) technique.
  • the ALD is based on a gas phase process where primary compounds are typically evaporated and pulsed into a reaction chamber separately. A thin film is generated when the material obtained from the reaction between the primary compounds is deposited on the surface to be coated. The material is deposited on the surface such that successive layers of molecule level are deposited one by one. This may be called “growing” of the material.
  • Thin film materials obtained by means of the ALD technique include, for example, metal oxides and metal nitrides.
  • a thin film coating is formed on the surface of silver by depositing successive molecule layers of one or more coating materials.
  • the ALD technique is adapted to coating an object comprising silver.
  • the object comprising silver is coated with a coating comprising aluminium oxide Al 2 O 3 .
  • any colourless metal oxide such as zirconium oxide ZrO 2 , titanium oxide TiO 2 , chromium oxide Cr 2 O 3 , indium oxide In 2 O 3 , niobium oxide Nb 2 O 5 , or any other material obtainable by the ALD technique may also be used.
  • FIG. 1 illustrates an embodiment of the present solution showing the coating of a silver surface S with aluminium oxide Al 2 O 3 .
  • the coating is built up of molecule layers of aluminium oxide.
  • FIG. 1 shows a situation where trimethyl aluminium (CH 3 ) 3 Al and water H 2 O are used as primary materials. If silver were coated with ZrO 2 , for example, ZrCl 4 and H 2 O might be used as primary materials.
  • step 1 - 1 the surface S is exposed to gas comprising trimethyl aluminium, in which case a layer of trimethyl aluminium molecules (CH 3 ) 3 Al is formed on the surface S.
  • step 1 - 2 the residual gas has been removed, and the layer comprising trimethyl aluminium molecules (CH 3 ) 3 Al remains on the surface S.
  • step 1 - 3 the surface S has further been exposed to water H 2 O.
  • trimethyl aluminium (CH 3 ) 3 Al and water aluminium oxide Al 2 O 3 is formed.
  • the reaction proceeds stepwise, and also other compounds may be formed, such as aluminium hydroxide AlOH and methane CH 4 .
  • aluminium oxide Al 2 O 3 is deposited on the surface S.
  • Step 1 - 4 shows a situation where unreacted trimethyl aluminium (CH 3 ) 3 Al and eventual other compounds have been removed, and there is a layer of aluminium oxide Al 2 O 3 deposited on the surface S.
  • the thin film coating of the present solution is obtained by growing of the material. This is carried out by repeating the steps 1 - 1 to 1 - 4 of FIG. 1 several times such that successive layers of aluminium oxide molecules are deposited on the surface S.
  • the thickness of the coating may be controlled by varying the number of molecule layers.
  • FIG. 2 illustrates a situation where the coating on the surface S of silver comprises four molecule layers of aluminium oxide Al 2 O 3 .
  • the number of successive layers of aluminium oxide Al 2 O 3 may be other than four.
  • the thickness of the coating is preferably within the range of 1 nanometer to 1 micrometer, more preferably within the range of 5 to 200 nanometers, most preferably about 10 nanometers.
  • the thickness of the coating may be adjusted by varying the number of the molecule layers of the coating material.
  • the one preferable thickness range is between 1 and 15 nm.
  • the yellowish appearance increases as the thickness of the coating increases (in range 0 to 50 nm) being very disturbing as the thickness of the coating is 20 nm or more.
  • the protective and/or passivating effect of the coating gets better as the thickness of the coating increases. Therefore, the thickness of the coating should be a compromise between the protection against tarnishing and the appearance of the silver product.
  • Another good thickness range is reached when the interference of the thin coating starts to intensify the blue color.
  • the blue color effect produced by the coating makes it brighter to the human eye.
  • This kind of effect may be produced with aluminum oxide deposited with ALD on a silver product when the thickness of the coating is in range about 60 to 90 nm. In this case also the passivation and/or protective effect of the coating is good.
  • the blue interference appears as a series also when the thickness of the coating is increased, but then also other colors may appear depending on the angle of view of the product and furthermore the processing of the silver product becomes slower and more expensive.
  • the above mentioned effect may also be achieved with other colourless or substantially colourless materials or coatings in addition to aluminium oxide.
  • the preferable thickness ranges vary according to material, because of the differences in the refractive index of the materials.
  • the lower of the mentioned thickness ranges (1-15 nm) requires ability to make very uniform and thin coatings as well as a low refractive index for the coating material. This is because of the fact that the yellowish appearance becomes a dominant feature before a sufficient thickness for the passivation and protection is achieved when materials having high refractive index are used. Aluminium oxide has proved to be one suitable material for providing thin uniform coatings to prevent tarnishing of a silver product when ALD is used. For example, when zirconium oxide is used, the appearance of a silver product becomes too yellowish before the sufficient passivation level is reached. A thin coating is preferable for the silver product. Then a material having low refractive index may be used.
  • ALD Advanced Deposition
  • the thickness of the substantially invisible coating produced by ALD may differ depending on the materials used such that the coating on a silver product is sufficient for producing a uniform and unbroken coating, but sufficiently thin for preventing discoloration of a silver product.
  • the optical dense is influenced, in addition to the refraction index, by reflectance factors, boundaries, imaginary components etc.
  • the temperature used in the coating process depends on the material properties. In many cases, it is advantageous to use a relatively high temperature. A high temperature allows molecules to evaporate readily, and a coating having a sufficiently good quality is obtained. According to the present solution, the coating temperature is preferably within the range of 80 to 400° C., more preferably within the range of 120 to 300° C., most preferably about 200° C.
  • Aluminum oxide process functions at least in a temperature range 100 to 250° C., and part even in a temperature range 20 to 300° C. These relatively low temperature ranges enable the coating for preventing tarnishing to be deposited after possible gemstones are planted and/or assembly solder joints or other assembly steps are conducted. Thus, all surfaces may be protected and there is no need to touch the surfaces with tools.
  • the low temperature also enables rapid processing of the silver products using these low temperatures, which also makes treatment more simple and advantageous.
  • the method is applied together with one or more protecting methods other than the method described herein.
  • the use of silver alloys that are resistant to oxidation, for example, may be applied.
  • the method is applied to coating silver-plated objects.
  • the method is applied to coating silver alloys.
  • the method is applied to coating objects or surfaces comprising bronze, copper and/or brass.
  • this same method may be used to coat also other metals so that the appearance of the metal is not influenced.
  • the method enables objects of various shapes to be coated. Thus it may be applied to coating jewels, ornaments, tableware, etc., as well as various industrial components.
  • aluminium oxide is not necessarily required by the present solution; any other coating material obtainable by the ALD technique, such as titanium oxide (TiO 2 ), tantalum oxide (Ta 2 O 5 ) and/or zirconium oxide (ZrO 2 ), may also be used. Different coating materials may be used simultaneously.
  • the obtained coating should have the desired properties and it should be compatible with the metal to be coated such as silver.
  • (CH 3 )Al also other compounds may be used as precursors, such as aluminium chloride AlCl 3 and/or triethyl aluminium (CH 3 CH 2 ) 3 Al.
  • water also other compounds, such as hydrogen peroxide H 2 O 2 , ozone O 3 , etc may be used as the oxygen source.
  • the choice of the coating material may depend on the application. For example, tableware or jewelry may require a biocompatible coating layer.
  • An example of a biocompatible coating material is aluminium oxide Al 2 O 3 . Reactions illustrated in FIG. 1 may occur in different order and also other reactions and/or steps may be carried out.
  • a coating having nanolaminate structure using ALD with two or more different coating materials. Then protective material is applied on the surface of a silver product such that one or more successive molecule layers are deposited and then another protective material is applied on the surface of a silver product such that one or more successive molecule layers are deposited. This may be continued until a predetermined coating thickness is achieved. It is also possible use three or more different materials in the mentioned successive manner. This provides a coating comprising two or more layers of two or more protective materials.
  • the applied coating is generally so thin that it is invisible to human eye.
  • the method may therefore be applied to silver jewelry, coins, medals, tableware, ornaments or the like silver products.
  • the method may also be applied to products comprising several different materials in addition to silver.
  • the method according to the present invention may be applied to at least part of an electronic or electrical component or other industrial component made of silver or silver alloys.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Physical Vapour Deposition (AREA)
  • Chemical Vapour Deposition (AREA)
  • Adornments (AREA)
  • Organic Insulating Materials (AREA)
  • Surface Treatment Of Glass (AREA)
  • Laminated Bodies (AREA)
US12/162,051 2006-02-02 2007-01-31 Protective coating of silver Active 2028-09-28 US8883258B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI20065082A FI121341B (fi) 2006-02-02 2006-02-02 Hopean suojapinnoitus
FI20065082 2006-02-02
PCT/FI2007/050056 WO2007088249A1 (en) 2006-02-02 2007-01-31 Protective coating of silver

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2007/050056 A-371-Of-International WO2007088249A1 (en) 2006-02-02 2007-01-31 Protective coating of silver

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/445,651 Continuation US20140335272A1 (en) 2006-02-02 2014-07-29 Protective coating of silver

Publications (2)

Publication Number Publication Date
US20090004386A1 US20090004386A1 (en) 2009-01-01
US8883258B2 true US8883258B2 (en) 2014-11-11

Family

ID=35953681

Family Applications (2)

Application Number Title Priority Date Filing Date
US12/162,051 Active 2028-09-28 US8883258B2 (en) 2006-02-02 2007-01-31 Protective coating of silver
US14/445,651 Abandoned US20140335272A1 (en) 2006-02-02 2014-07-29 Protective coating of silver

Family Applications After (1)

Application Number Title Priority Date Filing Date
US14/445,651 Abandoned US20140335272A1 (en) 2006-02-02 2014-07-29 Protective coating of silver

Country Status (12)

Country Link
US (2) US8883258B2 (de)
EP (2) EP2468921A1 (de)
JP (1) JP5297203B2 (de)
KR (1) KR101442850B1 (de)
CN (2) CN101379215A (de)
AT (1) ATE548482T1 (de)
AU (1) AU2007211451B2 (de)
DK (1) DK1994202T4 (de)
EA (1) EA012990B1 (de)
ES (1) ES2379892T5 (de)
FI (2) FI121341B (de)
WO (1) WO2007088249A1 (de)

Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200840880A (en) * 2007-04-13 2008-10-16 Hsin-Chih Lin Method of forming protection layer on contour of workpiece
FI20070991L (fi) * 2007-12-19 2009-06-20 Beneq Oy Lasituote, tuotteen käyttö ja valmistusmenetelmä
WO2010009467A2 (en) 2008-07-18 2010-01-21 Serenity Technologies, Inc. Method for producing nanocrystalline diamond coatings on gemstones and other substrates
DE102009041264A1 (de) 2009-09-11 2011-03-24 IPHT Jena Institut für Photonische Technologien e.V. Verfahren zur Herstellung von optisch aktiven Nanostrukturen
DE102009053889B4 (de) 2009-11-20 2014-03-27 C. Hafner Gmbh + Co. Kg Verfahren zur Beschichtung einer metallischen Substratoberfläche mit einer durch einen ALD-Prozess aufgebrachten Materialschicht
WO2011109807A2 (en) 2010-03-05 2011-09-09 Serenity Technologies, Inc. Method for imparting tarnish protection or tarnish protection with color appearance to silver, silver alloys, silver films, silver products and other non-precious metals
US20110236654A1 (en) * 2010-03-26 2011-09-29 Wen-Kuang Hsu Method of surface treatment and surface treated article provied by the same
CN102206810A (zh) * 2010-03-30 2011-10-05 徐文光 一种表面处理方法以及使用该方法的经表面处理的物品
JP5864089B2 (ja) 2010-08-25 2016-02-17 日亜化学工業株式会社 発光装置の製造方法
CN101974734B (zh) * 2010-11-30 2012-11-21 上海纳米技术及应用国家工程研究中心有限公司 具有多层复合防护膜的基底材料的制备方法
ITVR20120007A1 (it) * 2012-01-13 2013-07-14 Patros S R L Prodotto manufatto per la gioielleria e/o l'orificeria e/o la bigiotteria a base di ossido di zirconio e relativo metodo
US9334573B2 (en) 2012-01-16 2016-05-10 Hitachi Chemical Company, Ltd. Layered silicate silver surface treatment agent, sulfidation prevention film and light-emitting device with treated silver layer
JP5857786B2 (ja) 2012-02-21 2016-02-10 日亜化学工業株式会社 半導体発光素子の製造方法
DE102013100818B4 (de) 2013-01-28 2023-07-27 OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung Optoelektronischer Halbleiterchip und Verfahren zur Herstellung eines optoelektronischen Halbleiterchips
CN103757604A (zh) * 2013-12-25 2014-04-30 上海纳米技术及应用国家工程研究中心有限公司 用于银制品表面防护涂层的制备方法
US20150185382A1 (en) * 2013-12-31 2015-07-02 Saint-Gobain Performance Plastics Corporation Composite film having superior optical and solar performance
CN104060239B (zh) * 2014-06-06 2017-05-10 华中科技大学 一种金属物品表面保护方法
KR20170028419A (ko) * 2014-07-07 2017-03-13 씬트-엑스 에이비 박막 반사 장치의 제조
US11365481B2 (en) 2015-10-06 2022-06-21 City University Of Hong Kong Homogeneous and transparent protective coatings for precious metals and copper alloys
EP3173507A1 (de) * 2015-11-25 2017-05-31 Umicore AG & Co. KG Verfahren zur metallorganischen gasphasenabscheidung unter verwendung von lösungen von indiumalkylverbindungen in kohlenwasserstoffen
CN109121433A (zh) 2016-05-09 2019-01-01 Sage电致变色显示有限公司 包含用于防止离子迁移的装置的电致变色装置和及其形成方法
US10276411B2 (en) 2017-08-18 2019-04-30 Applied Materials, Inc. High pressure and high temperature anneal chamber
EP3768874A4 (de) * 2018-03-19 2022-03-30 Applied Materials, Inc. Verfahren zur abscheidung von beschichtungen auf komponenten der raumfahrt
US11015252B2 (en) 2018-04-27 2021-05-25 Applied Materials, Inc. Protection of components from corrosion
US11009339B2 (en) 2018-08-23 2021-05-18 Applied Materials, Inc. Measurement of thickness of thermal barrier coatings using 3D imaging and surface subtraction methods for objects with complex geometries
EP3626855A1 (de) 2018-09-21 2020-03-25 The Swatch Group Research and Development Ltd Verfahren zur verbesserung des glanzes einer versilberten abschlussoberfläche eines substrats, die gegen das anlaufen des silbers mit einer schutzschicht geschützt wird
EP3626854A1 (de) 2018-09-21 2020-03-25 The Swatch Group Research and Development Ltd Verfahren zur verbesserung der adhäsion einer schutzschicht gegen das anlaufen von silber auf einem substrat, das eine versilberte oberfläche umfasst
EP3626856A1 (de) 2018-09-21 2020-03-25 The Swatch Group Research and Development Ltd Substrat, das eine versilberte oberfläche umfasst, die gegen das anlaufen des silbers geschützt ist, und herstellungsverfahren eines solchen substrats
JP7312056B2 (ja) * 2019-01-07 2023-07-20 日機装株式会社 半導体発光素子および半導体発光素子の製造方法
CN109750273B (zh) * 2019-01-25 2020-01-21 中国地质大学（北京） 一种基于原子层沉积法进行镀膜改善银饰品稳定性的方法
WO2020219332A1 (en) 2019-04-26 2020-10-29 Applied Materials, Inc. Methods of protecting aerospace components against corrosion and oxidation
US11794382B2 (en) 2019-05-16 2023-10-24 Applied Materials, Inc. Methods for depositing anti-coking protective coatings on aerospace components
US11697879B2 (en) 2019-06-14 2023-07-11 Applied Materials, Inc. Methods for depositing sacrificial coatings on aerospace components
US11466364B2 (en) 2019-09-06 2022-10-11 Applied Materials, Inc. Methods for forming protective coatings containing crystallized aluminum oxide
CN111172511A (zh) * 2020-01-17 2020-05-19 胜科纳米（苏州）有限公司 一种在有机材料表面制备金属膜层的方法
US11519066B2 (en) 2020-05-21 2022-12-06 Applied Materials, Inc. Nitride protective coatings on aerospace components and methods for making the same
CN115734826A (zh) 2020-07-03 2023-03-03 应用材料公司 用于翻新航空部件的方法
KR102392451B1 (ko) * 2020-09-08 2022-04-29 국민대학교산학협력단 시냅틱 트랜지스터 및 이의 제조 방법
US12132110B2 (en) 2020-09-08 2024-10-29 Kookmin University Industry Academy Cooperation Foundation Synaptic transistor with long-term and short-term memory
US11185139B1 (en) * 2021-03-04 2021-11-30 Oujie Kevin Tong Coating compositions and method for jewelries

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH591566A5 (en) 1975-02-06 1977-09-30 Selve Usines Metallurg Suisses Transparent layer of amorphous alumina - applied to silver or silver plated objects for decorative or industrial applications
US4058430A (en) 1974-11-29 1977-11-15 Tuomo Suntola Method for producing compound thin films
US4413022A (en) 1979-02-28 1983-11-01 Canon Kabushiki Kaisha Method for performing growth of compound thin films
US4495254A (en) * 1981-05-18 1985-01-22 Westinghouse Electric Corp. Protectively-coated gold-plated article of jewelry or wristwatch component
JPS62180071A (ja) 1986-01-31 1987-08-07 Sumitomo Electric Ind Ltd 表面に透明硬質膜を有する貴金属製品
JPS63213655A (ja) 1987-02-27 1988-09-06 Nippon Dento Kogyo Kk 装身具
EP0679729A1 (de) 1994-04-29 1995-11-02 Wmf Württembergische Metallwarenfabrik Ag Verfahren zur Verhinderung des Anlaufens von Gegenständen
US6773757B1 (en) * 2003-04-14 2004-08-10 Ronald Redline Coating for silver plated circuits
US20040159830A1 (en) 2003-02-06 2004-08-19 Weimer Alan W. Nanomaterials for quantum tunneling varistors
US6897119B1 (en) 1999-12-22 2005-05-24 Genus, Inc. Apparatus and method to achieve continuous interface and ultrathin film during atomic layer deposition
US20060007677A1 (en) 1999-12-23 2006-01-12 Rajasingh Israel Optimal silicon dioxide protection layer thickness for silver lamp reflector

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09176868A (ja) * 1995-12-26 1997-07-08 Yoichi Murayama 銀製品への変色防止用透明保護膜形成法
JP4585852B2 (ja) 2002-07-30 2010-11-24 エーエスエム アメリカ インコーポレイテッド 基板処理システム、基板処理方法及び昇華装置
US20100123993A1 (en) * 2008-02-13 2010-05-20 Herzel Laor Atomic layer deposition process for manufacture of battery electrodes, capacitors, resistors, and catalyzers

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4058430A (en) 1974-11-29 1977-11-15 Tuomo Suntola Method for producing compound thin films
CH591566A5 (en) 1975-02-06 1977-09-30 Selve Usines Metallurg Suisses Transparent layer of amorphous alumina - applied to silver or silver plated objects for decorative or industrial applications
US4413022A (en) 1979-02-28 1983-11-01 Canon Kabushiki Kaisha Method for performing growth of compound thin films
US4495254A (en) * 1981-05-18 1985-01-22 Westinghouse Electric Corp. Protectively-coated gold-plated article of jewelry or wristwatch component
JPS62180071A (ja) 1986-01-31 1987-08-07 Sumitomo Electric Ind Ltd 表面に透明硬質膜を有する貴金属製品
JPS63213655A (ja) 1987-02-27 1988-09-06 Nippon Dento Kogyo Kk 装身具
EP0679729A1 (de) 1994-04-29 1995-11-02 Wmf Württembergische Metallwarenfabrik Ag Verfahren zur Verhinderung des Anlaufens von Gegenständen
DE4415122A1 (de) 1994-04-29 1995-11-02 Wmf Wuerttemberg Metallwaren Verfahren zur Verhinderung des Anlaufens von Gegenständen
US6897119B1 (en) 1999-12-22 2005-05-24 Genus, Inc. Apparatus and method to achieve continuous interface and ultrathin film during atomic layer deposition
US20060007677A1 (en) 1999-12-23 2006-01-12 Rajasingh Israel Optimal silicon dioxide protection layer thickness for silver lamp reflector
US20040159830A1 (en) 2003-02-06 2004-08-19 Weimer Alan W. Nanomaterials for quantum tunneling varistors
US6773757B1 (en) * 2003-04-14 2004-08-10 Ronald Redline Coating for silver plated circuits

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
Aug. 23, 2012, Office Action cited in JP 2008-552836 (with English translation).
Dicing Tape 1008 R: Silikonfrei, Laborprotokoll Reinigung and Beschichtung, Oct. 21, 2009, Selte 10 von 12.
Groner et al., "Electrical characterization of thin Al2O3 films grown by atomic layer deposition on silicon and various metal Substrates," Thin Solid Films, vol. 413, pp. 186-197, 2002.
Groner, M.D. et al., "Electrical characterization of thin Al2O3 films grown by atomic layer deposition on silicon and various metal substrates," Thin Solid Films, 413 (2002) pp. 186-197.
Mar. 16, 2010 Search Report issued in European Application No. 07704826.2.
Matero et al., "Atomic layer deposited thin films for corrosion protection," Journal of Physics IV, vol. 9, No. 8, Pt. 1, pp. 493-499, Sep. 1999.
Matero, R., "Atomic Layer Deposition of Oxide Films-Growth, Characterisation and Reaction Mechanism Studies," Academic Dissertation, Helsinki (2004).
Nov. 12, 2012 Notice of Opposition (with Annex) issued in European Application No. 07704826.2.
Pilvi, T., "Atomic Layer Deposition for optical applications: metal fluoride thin films and novel devices," Academic Dissertation, Helsinki (2008).
Ritala et al., "Atomic Layer Deposition," Chapter 2, ISBN 0-12-512909-2, Helsinki (2002), pp. 103-159.
Spectra Technology Inc., "Grazing Incidence Absorption Measurements," Final Report 9-X18-8599Q-1 (1989).
Suntola (Handbook of Crystal Growth, vol. 3, edited by D.T.J. Hurle (1994), pp. 601-608). *
Translation of Mar. 11, 2010 Office Action issued in Chinese Patent Application No. 200780004086.3.

Also Published As

Publication number Publication date
EA012990B1 (ru) 2010-02-26
JP2009525406A (ja) 2009-07-09
US20090004386A1 (en) 2009-01-01
FI20065082A (fi) 2007-08-03
US20140335272A1 (en) 2014-11-13
ES2379892T5 (es) 2020-06-18
FI20065082A0 (fi) 2006-02-02
JP5297203B2 (ja) 2013-09-25
DK1994202T4 (da) 2020-02-03
FI10853U1 (fi) 2015-04-27
AU2007211451B2 (en) 2011-08-11
FI121341B (fi) 2010-10-15
ES2379892T3 (es) 2012-05-04
CN103215560A (zh) 2013-07-24
CN101379215A (zh) 2009-03-04
DK1994202T3 (da) 2012-04-02
EP1994202A4 (de) 2010-04-14
EP2468921A1 (de) 2012-06-27
KR101442850B1 (ko) 2014-11-19
KR20080103517A (ko) 2008-11-27
EP1994202B2 (de) 2019-12-18
EA200870142A1 (ru) 2009-02-27
ATE548482T1 (de) 2012-03-15
AU2007211451A1 (en) 2007-08-09
EP1994202A1 (de) 2008-11-26
EP1994202B1 (de) 2012-03-07
WO2007088249A1 (en) 2007-08-09

Similar Documents

Publication Publication Date Title
US8883258B2 (en) Protective coating of silver
JP4964892B2 (ja) 装飾部品およびその製造方法
US5853826A (en) Method of improving the color of transparent materials
EP2371993A1 (de) Verfahren zur Oberflächenbehandlung und damit bereitgestellter oberflächenbehandelter Artikel
JP7297031B2 (ja) 時計仕掛けの構成要素などのアイテムにコーティングを堆積するための方法、およびそのような方法によってコーティングされたアイテム
US20130130044A1 (en) Method for forming a decorative coating on a gemstone, a decorative coating on a gemstone, and uses of the same
JP2020097213A (ja) 銀面を有する基材に対する曇りから銀を保護する層を接着させて材料を作る方法
CN113930721A (zh) 一种红铜金色pvd装饰薄膜及其制备方法
CN212199411U (zh) 包括受保护以防褪色的银表面的基材
KR102640464B1 (ko) 간섭 컬러 코팅을 포함하는 타임피스 또는 보석류의 피스용 외부 부품 및 상기 부품의 제조 방법
KR20200118703A (ko) 색채화된 표면을 가지는 금속부재 및 금속 표면의 색채화 방법
CN116381825B (zh) 复合材料结构件及其加工方法、电子设备
CN113549872B (zh) 黑色涂层
Guzman et al. Coloration of metallic and/or ceramic surfaces obtained by atomic layer deposited nano-coatings
US20240360048A1 (en) External part made of ceramic material comprising a protective layer and method for producing such an external part
PL240326B1 (pl) Sposób wytwarzania warstwy ochronnej z efektem optycznym na powierzchni przedmiotów metalowych
CN112835140A (zh) 彩色膜层
JPH0339102A (ja) 板状金属装飾品または同様なバツジ、メダルまたは文字盤
PL240327B1 (pl) Sposób wytwarzania powłok antyalergicznych na powierzchni przedmiotów codziennego użytku
JPS6153240B2 (de)
JP2001303234A (ja) 硬質保護膜
JPH01152257A (ja) 装飾用薄膜およびその形成方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: BENEQ OY, FINLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MAKELA, MILJA;SOININEN, PEKKA;SNECK, SAMI;REEL/FRAME:021492/0588;SIGNING DATES FROM 20080804 TO 20080806

Owner name: BENEQ OY, FINLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MAKELA, MILJA;SOININEN, PEKKA;SNECK, SAMI;SIGNING DATES FROM 20080804 TO 20080806;REEL/FRAME:021492/0588

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551)

Year of fee payment: 4

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 8